Reaction products of an aldehyde and a triazole derivative



rmsdse teiass am REACTION PRODUCTS AN ALDEIIYDE AND A rarazou DIBIVA rrvr:

Gaetano F. DAlello, Plthflell, Mala, aoslmr to General Electric m!- a corporation or New York No Drawlnt.

This invention relates to the production oi new synthetic materials and especially to new reaction products havins particular utility inthe plastics and coating arts. Specifically the invention is concerned with compositions oi matter comprising a condensation product 01 ingredients comprising an aldehyde, including P lymerlc aldehydes, hydroxy-aldehydes and aldehyde-addition products, e. 5., formaldehyde, paraformaldehyde, aldol, glucose, urea, trimethylol melamine, etc.. and a triaaole derivative corresponding to the following general formula:

In. the above formula R represents a member of the class consisting of hydrogen and monovalent hydrocarbon radicals, R represents a monovalent hydrocarbon radical, and Z represents a member or the class consisting of divalent aromatic and nuclearly substituted, more particularly nuciearly halogenated. aromatic hydrocarbon radicals. Instead of the derivatives of the 1,2,4-triasoies represented by the above formula, corresponding derivatives of the 1,2,3-triazoles, the 1.2,5-triazoles or of the l.3.4-triazoles may be employed.

Illustrative examples or monovalent hydrocarbon radicals that R and R in the above formula may represent are: aliphatic (e. 3., methyl, ethyl, propyl, isopropyl, butyl, secondary butyl, isobutyl, butenyl, amyl, isoamyl, hexyl, octyi, allyl, methallyl, crotyi, etc), including cycloaliphatic (e. g., cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, cycloheptyl, etc); aryl (e. 8.. Dhenyl, dipli'enyl or xenyl, naphthyl, anthracyl, etc); aliphatic-substituted aryl (e. g.. tolyl, xylyl, ethyiphenyl, propylphenyl, isopropwlphenyl, ally]- phenyl, z-butenylphenyl, propenylphenyl, tertiary-butylphenyl, methylnaphthyl, etc.) and aryl-substituted aliphatic (e. g., benzyl, cinnamyl, phenylethyl, phenylpropyl, etc). Preterably It represents hydrogen, in which case the compounds correspond to the following general i'ormula:

where Z and B have the same meanings as given above with reference to Formula 1. However,

tion December 28, 1942,

Applloa Berhl No. 410.219

dimethyloi l0 therealsomaybeusedinpracticingthepresent 5t invention chemical compounds corresponding to the following general iormulas:

and

where R, R and Z have the same meanings as given above with reference to Formula I.

Illustrative examples of divalent radicals th t Z in the above formulas may represent are: divalent aromatic, e. g., phenylene, xenyiene, naphthylene, etc.; divalent aliphatic-substituted aromatic, e. 3., 2,4-tolylene, ethyl 2,5-phenyiene, isopropyl 3,4-phenylene, l-butyi 2,4-naphthylene, 1,4-dimethyl 2,3-phenylene, etc.; radicals that may be classed either as divalent aliphatic-substituted aromatic or as divalent aromatic-sum stituted aliphatic and wherein the tree bond of the aromatic nucleus is attached to the acyl amino radical, e. 3., 4,9.1pha-tolylene, 3,beta-phenyleneethyl, 4,alpha xylylene, 2.gamma phen ylenehutyl, etc.: and their homologues, as well as those divalent radicals with one or more of their nuclear hydrogen atoms replaced by a substituent, e. g., acyl, alkyl, alkenyl, hydroxy, alkor v. aryloxy, carboalkoxy, carboaryloxy, suliamyl, an

Emil-Ping in addition to the single acylamino grouping shown, to: example. in Formula 1, etc. Bpeciiic examples of substituted divalent radical that Z may represent are chlorophenylene, bromophenylene, chloroxenylene, chloronaphthyione, chlorotolylene, bromotolylene, ethoxyphenyh ene, scetophenylene, acetoxyphenylene, aminophenylene, carboethoxyphenylene, sulfamylphenylene, carbophenoxyphenylene, hydroxyphenylene, phenoxyphenylene, methylphenyiene (tolylene), allyiphenylene, etc. Preferably Z is phenylene or tolylene.

The triazole derivatives that are employed in carrying the present invention into effect are more fully described and are specifically claimed in my copending application Serial No. 470,220, filed concurrently herewith and assigned to the same assignee as the present invention. As pointed out in this copendine application, a

method of preparing the triazole derivatives LJEBd in practicing the present invention comrises effecting reaction under heat between a hydrazine corresponding to the general formula NHz-NHR, where R has the same meaning as iven above with reference to Formula I, and an acylaminoaryl biguanide corresponding to the eneral formula NE NH where R. R and Z have the same meanings as given above with reference to Formula I. The reaction is carried out under conditions such as will result in the formation of ammonia. or, ii an acid is present, an ammonium salt as a byproduct of the reaction.

The specific examples of compounds embraced by Formula I that may be used in practicing my invention are listed below:

The (acetamido aniline) amino 1,2,4-triazoies. including 3-(ortho-acetamido anilino) fl-amino 1,2,4-triazole; 3-amino 5-(ortho-acetamido aniline) 1,2,4-triazole: 3-(meta-acetamido aniiino) 5-amino 1,2,4-triamle; 3-a-miao b-(metaacetamido aniline) 1,2.4-triaaole; 3-(para-acetamido aniline) 5-amino 1,2,4-triaaole; and 3- amino 5-(para-acetamido aniline) IRA-triazole l-methyl B-(Ortho-acetamido anilino) 5-amir1o i,2,4-triazole l-methyi 3-amino S-(ortho-acetamido aniline) 1,2,4-triazle l-methyi S-(meta-acetamido anilino) ii-amino 1,2,4 -triazoie i-methyl 3-amino -(meta-acetamido aniline) 1,2,4-triazole i-methyl 3-(para-acetamido anilino) fi-amino 1,2,4-triaz01e i-methyl 3-amino 5-(para-acetamido aniiino) 1.2,4-trlazole l-phenyl 3-(ortho-acetamido aniline) fi-amino 1,2,4-triazo1e i-phenyl 3-amino 5-(ortho-acetamido aniline) 1,2,4-triazole l-phenyl 3-(meta-acetamido 1,2,4-triaz01e l-phenyi 3-aminc fi-(meta-acetamido anilino) 1 ,2,4-triazole l-phenyi 3-(para-acetamido aniline) fi-amino 1,2,4-triazole l-phenyi B-amino 5-(para-acetamido anilino) 1,2.4-triazo1e iPara-propanamido anilino) amino Lzbtriazoles iiN-methyi acetamido) aniline] amino 1,2,4-

triazoles [(N-isobutyl benzamido)xyenylamino] amino 1,2,4-triaz01es [(N-phenyl benzamido) anilino] amino 1,2,4-

triazoles :(N-cyelopentyi acetamido) aniiino] amino 1,2,4-

anilino) S-amino triazoles [(N-tolyl acetamido) toluido] amino 1,2,4-triazoles l-ethyl 3-(ortho-acetamido anilino) S-amino 1,2,4-triazo1e i-ethyl 3-amino 5-(ortho-acetamido anilino) 1,2,4-triazole l-ethyl 3-(meta-acetamido anilino) 5-amino 1,2,4-triazo1e l-ethyl 3-amino S-(meta-acetamido anilino) 1,2,4-triazole l-tolyi 3-(ortho-acetamldo aniline) fi-amino 1,2,4-triazole 1-toiyl B-amino 5-(ortho-acetamido anilino) 1,2,4-tz1azule l-toiyl :i-(meta-acetamido anilino) S-amino 1,2,4-triazole l-tolyl 3-amino 5-(meta-acetamido anilino) 1,2,4-triazole (Ortho-propanamido aniline) amino 1,2.4-trimoles (Meta-propanamido anilino) amino 1,2.4-triaaolea (Acetamido toiuldo) amino 1.2,4-trlazoles l-butyl (acetamido anilino) amino 1,2,4-triazoles l-methyl (acetamido toluido) amino 1,2,4-tri- (Acetamido ethyl aniline) amino 1,2.4-triazoies (Benzamido methyl naphthylamino) amino 1.2,4-triazoles (Dimethylbenzamido nuoro aniline) amino 1,2,4-

triazoles (Naphthamido anilino) amino 1,2,4-triazoles i-propyl (acetamido toluido) amino 1,2,4-triazoles l-isobutyl (benzamido aniiino) amino 1,2,4-triazolca i-propenyl (benzamido aniline) amino 1,2,4-triazoles l-cyclopentyl (acetamido aniline) amino 1,2,4-

triazoies l-phenyi (methyibenzamido xylidino) 1,2,4-triazoles l-methyl [(N-methyl acetamido) anilino] amino 1,2,4-triazolea l-benzyl [(N-ethyl acetamido) aniline] amino 1,2,4-triazoles (Aoetamido chloro aniline) amino 1,2,4-triazoles (Acetamido hromo aniiino) amino 1,2,4-triazoles (Propanamido iodo toluido) amino 1,2,4-triazoies (Butanamido fluoro toluido) amino 1,2,4-triazo1es l-phenethyi (acetamido anilino) amino 1,2,4-

triazoles i-ethylphenyl (acetamido anilino) amino 1,2,4-

triazoles [(N-phenyl acetamido) anilinol amino 1,2,4-

triazolea [(N-ethyi propanamido) anilinol amino 1,2,4-

triazoles [(N-propyl butanamido) toluido] triazoles i-methyl [(N-allyi acetamido) anilino] amino 1,2,4-triazoles i-methyi [(N-methyl acetamido) naphthylamiamino LzA-triazoles I-phenyl [(N-phenyi acetamido) anilinol amino 1,2,4-triazolea l-tolyl [(N-bcnzyl acetamido) propyi anilinol amino 1,2,4-triamles l-ethyl iiN-phenethyl acetamido) holuido] amino 1,2,4-triazolea i-allyl (acetamido anilino) amino 1,2.4-triazolea It will be understood, 01' course, by those skilled amino amino 1,2,4-

in the art that, in those compounds listed above which are generically named, the amino groupme my be attached to either the 3 or the 5 carbon atoms oi the triazole nucleus, the carbon atom which is not Joined to an amino grouping being attached to the acylaminoarylamino grouping; and, also, that the acylaminc grouping may be attached to any of the reactive carbon atoms of the aromatic nucleus.

The present invention is based on my discovery that new and valuable materials having particular utility in the plastics and coating arts can be produced by effecting reaction between ingredients comprising essentially an aldehyde, including polymeric aldehydes, hydroxyaldehydes and aldehyde-addition products, and a triazole derivative of the kind embraced by Formula I, numerous examples of which have been given above and in my copending application Serial No. 470,220.

Resins made by condensin an aldehyde with guanazole (3,5-diamino 1,2,4-triazole) and l-substituted guanazoles, e. g., 1-phenylguanazole,are not entirely satisfactory for use in many applications, for instance in the production of molding compounds having a. high plastic flow combined with a rapid cure under heat to an insoluble, iniuslble state. Surprisingly it was found that the heat-curable resinous condensation products of this invention and molding compositions made therefrom show excellent flow characteristics during a short curing cycle. This is a property that is particularly desirable in a thermosetting resin and molding compound. The molded artlcles have a high dielectric strength and excellent resistance to arcing. They have a good surface finish and, in most most cases, a better resistance to water than the ordinary urea-aldehyde resins. The cured resins have a high resistance to heat and abrasion. Hence they are especially suitable for use where optimum heatand abrasion-resistance are of primary importance.

In practicing my invention the initial condensation reaction may be carried out at normal or at elevated temperatures, at atmospheric, subatmospheric or super-atmospheric pressures, and under neutral, alkaline or acid conditions. Preferably the reaction between the components is initiated under alkaline conditions.

Any substance yielding an alkaline or an acid aqueous solution may be used in obtaining alkaline or acid conditions for the initial condensation reaction. For example, I may use an alkaline substance such as sodium, potassium or calcium hydroxides, sodium or potassium carbonates, mono-, dior tri-amines, etc. In some cases it is desirable to cause the initial condensation reaction between the components to take Place in the presence of a primary condensation catalyst and a secondary condensation catalyst. The primary catalyst advantageously is either an aidehyde-non-reactable nitrogen-containing basic tertiary compound, e. g., tertiary amines such as trialkyl (e. g., trlmethyl, triethyl, etc.) amines, trlaryl (e. g., trlphenyl, tritolyl, etc.) amines, etc.. or an aldehyde-reactable nitrogen-containing basic compound, for instance ammonia, primary amines (e. g., ethyl amine, propyl amine, etc.) and secondary amines (e. g., dipropyl amine, di-

butyl amine, etc), The secondary condensation catalyst, which ordinarily is used in an amount less than the amount of the primary catalyst, advantageously is a fixed alkali, for instance a carbonate, cyanide or hydroxide of an alkali metal (e, g., sodium, potassium, lithium, etc).

Illustrative examples or acid condensation catalysts that may be employed are organic and inorganic acids such as hydrochloric, sulfuric, phosphoric, acetic, lactic, acrylic, malonic, etc., and acid salts such as sodium acid sulfate, monosodlum phosphate, monosodium phthalate, etc. Mixtures of acids, of acid salts or of acids and of acid salts may be employed if desired.

The reaction between the aldehyde, e. formaldehyde, and the triazole derivative may be carried out in the presence or absence of solvents or diluents, fillers, other natural or synthetic resinous bodies or while admixed with other materials that also can react with the aldehydlc reactant or with the triazole derivative, e. g., ke tones, urea, thiourea, sclenourea, lminourea (guanidine) substituted ureas, thioureas. selenoureas and iminoureas, numerous examples of which are given in various copending applications of mine, for instance in my copending application Serial No. 363,037, filed October 26, 1940, now Patent No. 2,322,566, issued June 22, 1943; monoamides of monocarboxylic and polycarboxylic acids and {Jolt/amides of polycarboxylic acids, e. g., acetamide, halogenated acetamides (e. g., a chlorinated acetamide), maleic monoamide, malonic monoamide, phthalic monoamide, maleic diamide, fumaric diamide, malonic diamide, itaconic diamide, succinic diamide, the monoamide, diamide and triamide of tricarballylic acid, etc.; aminotriazines, e. g., melamine, ammeline, ammelide, melem, melam, melon, numerous other examples being given in various copending applications oi mine, for instance in application Serial No. 377,524, filed February 5, 1941, and in applications referred to in said copending application; phenol and substituted phenols, e. g., the cresols, the xylenols, the tertiary alkyl phenols and numerous other phenols such as mentioned in my Patent No. 2,239,441, issued April 22, 194i; monohydric and polyhydric alcohols, e. g., butyl alcohol, amyl alcohol, isoamyl alcohol, heptyl alcohol, octyl alcohol, 2-ethy1butyl alcohol, ethylene glycol, glycerine, polyvinyl alcohol, etc.; amines, including aromatic amines, e. g., aniline, etc.; and the like.

The modifying reactants may be incorporated with the triazole derivative and the aldehyde by mixing all the reactants and effecting condensation therebetween or by various permutations of reactants as described, for example, in my Patent No. 2,281,559, issued May 5, 1942 (page 2, column 1, lines 46-49), with particular reference to reactants involving a non-haloacylated urea, a haloacylated urea and an aliphatic aldehyde. For instance, I may form a partial condensation product of ingredients comprising (1) urea or melamine or urea and melamine, (2) a trlazole derivative of the kind embraced by Formula I, e. g., an (acetamido aniline) amino 1,2,4-triazole [(ortha-, metaor para-acetamido aniline) amino 1,2,4-triazole], which also may be named (acetamido phenylamino) amino 1,2,4-triazole and which includes within its meaning 3- (ortho-, metaor para-acetamido anilino) 5-amino l,2,4- triazole and 3-amino 5-(ortho-, metaor paraacetamido aniline) 1,2,4-triazole, a l-alkyl (acetamido aniline) amino 1,2,4-triazole, a l-aryl (acetamido anilino) amino 1,2,4-triazole, etc, and (3) an aldehyde, including polymeric aldehydes, hydroiwaldehydes and aldehyde-addition products, for instance formaldehyde, paraformaldehyde, glyceraldehyde, dimethylol urea, a polymethylol aminotriazine, e. g., trimethylol melamine, hexamethylol melamine, etc. Thereafter 1 further by the removal may eilect reaction between this partial condensation product and. for example, a curing reactant, specifically a chlorinated acetamide, to obtain a heat-curable composition.

Some oi the condensation products oi this invention are thermoplastic materials even at an advanced stage condensation, while others are thermosetting or potentially thermosetting bodies that convert under heat or under heat and pressure to an insoluble, ini'usible state. The thermosetting or potentially thermosetting resinous condensation products, alone or mixed with iillers, pigments, lubricants, plasticizers, curing agents. etc., may be used, for example, in the production 01' molding compositions. The thermoplastic condensation products are of particular value as plasticizers for other synthetic reshis The liquid intermediate condensation products this invention may be concentrated or diluted or addition oi volatile solvents to form liquid coating compositions of adjusted viscosity and concentration. The heatconvertible or potentially heat-convertible resinous condensation products may be used in liquid state, for instance as surface-coating materials, in the production of paints, varnishes, lacquers, enamels, etc., for general adhesive applications. in producing plywood (bonded sheets of wood veneer) and other laminated structures, and for numerous other purposes. The liquid heat-hardenable or potentially heat-hardenable condensation products also may be used directly as casting resins, while those which are of a gellike nature in partially condensed state may be dried and granulated to term clear, unfilled heatconvertible resins.

In order that those skilled in the art better may understand how the present invention may be carried into effect, the following examples are given by way or illustration and not by way oi limitation. All parts are by weight.

Example 1 Parts (Para-acetamido aniline) amino 1,2,4-triazole 232 Aqueous formaldehyde (approx. 37.1%

HCHO) 243 Aqueous ammonia (approx. 28% NHs) 30 Sodium hydroxide in 50 parts water 1 were heated together under reflux at the boiling temperature or the mass for 30 minutes. yielding a resinous syrup. A thermosetting resin was obtained by incorporating chioroacetamide (monochloroacetamide) glycine, suli'amic acid or other curing agent such as hereafter mentioned either into the initial syrupy condensation product or into the dehydrated syrup.

To 115 parts of the syrup prepared as above described was added 0.5 part suli'amic acid, after which the mixture was heated under reflux at boiling temperature for 5 minutes. The resulting hot, resinous syrup was mixed with 35 parts alpha-cellulose in flock form and 0.2 part or a mold lubricant, specifically zinc stearate. to form a molding (moldable) composition. The wet molding compound was dried at 65 C. for two hours. A sample of the dried and ground molding composition was molded for 5 minutes at 130 C. under a pressure oi 2,000 pounds per square inch. The molded piece was strong and well cured throughout and had a well-knit and homogeneous structure The plasticity of the molding compound during molding was very good. Instead of using suli'amic acid in accelerating duced by adding to the partial condensation prodnot (in syrupy or other form) direct or active curing catalysts (e. g., citric acid, phthalic anhytions of mine, for instance in my copending application Serial No. 346,962, filed July 23, 1940,

Example 2 Parts (Para-acetamido aniline) amino 1,2,4-triazole 46.4 Urea 48.0 Aqueous formaldehyde (approx. 37.1

HCHO) 162.0 Aqueous ammonia (approx. 28% NH3) 10.0 Sodium hydroxide in 5 parts water 0.1

were heated together under reflux at boiling temperature for 15 minutes, yielding a gel. When a sample of this gel was heated on a 140 C. hot plate, it bodied to a thermoelastic resin. This resin was potentially heat-curable as shown by the fact that when a small amount of a curing a 140 C. hot plate, the material was converted into an insoluble and ini'usible state.

After mixing 1 part chloroacetamide (monochloroacetamide) with parts of the initial condensation product, the resulting mixture was refluxed for 5 minutes. A molding composition was prepared from the chloroacetamide-modiiled syrup in the same manner as described under Example I with reference to the sulfamic acidmodifled syrup of that example with the exception that the time of drying at 65 C. was only 1 hour. A well-molded piece having good strength and an attractive surface appearance was obtained by molding a sample of the dried and ground molding compound for 5 minutes at C. under a pressure or 2,000 pounds per square inch. The molding composition showe good plasticity during moi ding.

Example 3 Parts (Para acetamldo anilino) amino 1,2,4-triazole 232 Para-toluene sulionamide 171 Aqueous formaldehyde (approx. 37.1%

HCHO) 324 Sodium hydroxide in 50 parts water 1 assaseo were heated together under reflux at the boilins emu ai'tsr modification with a curing agent. may temperature oi the mass for 30 minutes. yieidina be used in the production or molding compounds. a clear syrup. The incorporation of a small gum," amount gm I., chlotrgaiietamig; Pm glycine. c d, cures, e nto syrup, followed by heating on a 140' 0. hot plate. a 't m :33 caused the syrup to convert into an insoluble and m I iniusibleorcuredresin. am"

To 110 parts of the syrup produced as above do hydroxide in 5 M scribed was added 0.5 port suliamilc acid, after f which the mixture was refluxe ior 5 minutes. A were heated tolether under reflux at boilins molding composition was prepared from this .l tm' r minutes. yieldins a water-luck Example 1 with the. able resin hsvin: cur-ins characteristics much the syrup as described under ception that the wet molding compound was dried for 1 hour at 84 C. A sample of the dried and ground molding composition was molded for 5 minutes at 130 C. under a pressure of 2,000 pounds per square inch. The molded piece was well cured throughout and had a well-knit and homoseneous structure. The molding compound showed excellent plastic iiow during molding as evidenced by the amount of flash on the molded article.

Emilie 4 Parts Synthetic phenol 45.0 Aqueous formaldehyde (approx. 37.1%

H080) 07.5 Potassium carbonate 1.43 (Para-acetamido aniline) amino 1.2,4-tri- Mole 4.

A liquid phenol-formaldehyde partial condensation product was prepared by heating together. all of the above insredients with the exception oi the triazole derivative under reflux for 3% hours at 05 to 10 C. The above-stated amount or (para-acetamido anilino) amino 1,2,4-triasole was added to this syrupy phenolic resin and heatin: under reilux was continued for 1 hours. At the end of this reaction period the resulting syrupy intercondensation product was acidified by adding thereto 3 parts oxalic acid dissolved in parts water. A molding compound was made from the acidiiled syrup parts alpha-cellulose an 0.6 part zinc stearate. The wet molding composition was dried for 2 hours at C. A well-cured, light-colored molded piece having good water resistance was obtained by molding a. sample of the dried and ground molding composition for 5 minutes at C. under a pressure of 2,000 poundsper square inch. Satisfactory plastic ilow during molding was indicated by the amount of flash on the molded article.

Example 5 Parts (Para-acetamido anilino) amino 1,2,4-triazole 28.2 Furmral 28.8 Aqueous ammonia (approx. 28% NI-Ia) 2.0 Sodium hydroxide in 5 parts water 0.1 Water 50.0

were heated together under reflux at the boiling temperature of the mass for 30 minutes, yielding a. very viscous. resinous mass. This resin cured to an insoluble and infuslble state in the absence of a curing agent when a small sample 01' it was heated on a 0. hot plate. The curing of the resin was accelerated by incorporating glycine. citric, acid, chloroacetamide Or other curingagent such as mentioned under Example 1 into the heatcurable resin prior to heating on the hot plate. The resinous composition oithls example, espeby mixing therewith. 5'1

sameastheresinoimmpleb. Asinthecase o! the resin of Example 5, the resinous composition oi this example likewise is suitable for use in the preparation 0! molding compounds.

' Example 7 Parts (Para-acetamido aniline) amino 1,2,4-trb amle Butyl oi 74 0 Aqueous formaldehyde (approx. 3'1 1% ECHO) 64.8 Sodium hydroxide in 5 parts water 0.1

The above ingredients were heated together under reflux at the boiling temperature or the mass ior 30 minutes, yielding a clear. syrupy condensation product. This syrup bodied to a thermoplastic resin when a sample of it was heated on a 140 0. hot plate. This resin was potentially heat-curable as shown by the tact that when sulfa-mic acid, citric acid. chloral urea. glycine, phenacyl chloride. chloroacetamide, nitrourea or other curins asent such as mentioned under Example was added either to the syrupy condensation product or to the thermoplastic resin, followed by heating on a 140 C. hot plate, the material cured to an insoluble and infusible state. The dehydrated resin was alcohol-soluble. The cured resin displayed marked resistance to water, alcohols, etc. The resinous composition of this example is especially suitable for use in the preparation oi liquid coating and impregnating materials.

Example 8 Parts (Para-acetarnido aniline) amino 1,2,4-triazole 23.2 Acctamide 5.9 Aqueous iormaldehyde (approx. 37.1%

HCHO) 40.5 Aqueous ammonia (approx. 28% NHs) 3.0 Sodium hydroxide in 5 parts water 0.1

were heated together under reflux at the boiling temperature of the mass for 30 minutes, yielding a clear, viscous syrup that bodied to a thermoplastic resin when a sample of it was heated on a 140 C. hot plate. This resin was potentially heat-curable as shown by the fact that the addition 0! a small amount of suliamic acid, citric acid, oxalic acid. chloroacetamide, glycine or other curing agent such as mentioned under Example 1 to the initial syrup or to the thermoplastic resin. followed by heating on a. 140 C. hot plate, caused the material to convert to a cured or insoluble and iniusibie state. The excellent plastic flow o! the resin during curing indicated that it would be particularly suitable for use as a plasticizer of less plastic aminoplasts and other compatible resins to improve their plasticity or flow characteristics. For example, it

may be used as a modifier oi. urea-aldehyde resins, melamine-aldehyde resins; aniline-aldehyde resins, etc., the flow characteristics oi which are unsatisfactory during curing, to improve the piesperature for 30 minutes, yielding a syrupy condensatlon product that bodied to a thermoplastic resin when a small sample or it was heated on a 140 C. hot plate. Heat-curable resins are pre-- pared by incorporating chloroacetamide. glycine or other curing agent such as mentioned under Example 1 into the initial syrup or into the thermoplastic resin. The resinous material of this example may be employed in the preparation oi various varnish compositions. Because of its inherent plastlcizing characteristics, it also may be used as a flow extender for other compatible aminoplasts and other synthetic resins having unsatisfactory flow characteristics.

Example 10 Parts (Para-acetamido anilino) amino 1,2,4-triazole 23.2 Polyvinyl alcohol 20.4 Aqueous formaldehyde (approx. 37.1%

HCHO) 64.8 Sodium hydroxide in 5 parts of water- 0.1 Water 100.0

The above ingredients were heated together under reflux at boiling temperature for 30 minutes. When a sample oi the resulting syrupy condensation product was heated on a 140-150 C. hot plate, it bodied to thermoelastic resin. The pH of the syrup was lowered by adding thereto a small amount 01' an acid, specifically hydrochloric acid. The acidified syrup was thermosettlng, as evidenced by the fact that it cured to an insoluble and infusible state when a small sample or it was heated in film form at 70 to 80 C. for several hours. The baked film was hard and tough, and showed good resistance to water. Instead of hydrochloric acid, other ouring agents such as mentioned under Example 1 may be employed to improve the curing characteristics and the water resistance of the resinous material of this example. The thermoplastic resinous product. either with or without a curing agent, may be used in the preparation various liquid coating and impregnating compositions. The thermosettlng resins may be empioyed in the production of molding compounds.

Example 11 Parts (Para-acetamido aniline) amino 1,2,4-triazole 23.2 Diethyl malonate 16.0

Aqueous formaldehyde (approx. 37.1%

HCHO) 40.5 Aqueous ammonia (approx. 28% NH!) 3.0 Sodium hydroxide in parts water 0.1

The above ingredients were heated together under reflux at the bo ling temperature of the mass for 30 minutes. when a sample of the resulting resinous syrup was heated on a 140 hot plate, it bodied to a thermoplastic resin. The addition otasmallamountofacurlngasentsuch as mentioned under Example 1 either to the syrupy condensation product or to the thermoplastic resin, tollowed by heating on a 140' 0. hot plate, caused the material to cure to an iniusible, insoluble resin. The resinous mass exhibited a long period of iiow during curing. indicating that the resin of this example would be particularly adapted for use as a now extended for other compatible aminoplast resins.

It will be understood, of course, by those skilled in the art that the reaction between the aldehyde and the triazole derivative may be eflected at temperatures ranging, for example, from room temperature to the fusion or boiling temperature of the mixed reactants or of solutions 01' the mixed reactants, the reaction proceeding more slowly at normal temperature than at elevated temperatures in accordance with the general law or chemical reactions. Thus, instead or eifecting reaction between the insredients oi the above examples under reflux at the boiling temperature of the mass as mentioned in the individual examples, the reaction between the components may be carried out at lower temperatures, for exam pic at temperatures ranging from room temperature to a temperature near the boilin temperature using longer reaction periods and, in some cases, stronger catalysts and higher catalyst concentrations.

It also will be understood by those skilled in the art that my invention is not limited to condensation products obtained by reaction oi ingredients comprising an aldehyde and the specific triazole derivative embraced by Formula I that is named in the above illustrative examples. Thus, instead of a (para-acetamido aniline) amino 1,2,4-triazole I may use, for example, an (ortho-acetamido anilino) amino 1,2,4-triazole, more particularly 3- (ortho-acetamido aniiino) 5-amino 1,2.4-trlazole or 3-amino 5- (ortho-acetamido aniline) 1,2,4-triazole, a (meta-acetamido aniline) amino 1,2,4-triazole, specifically 3- (metaacetamido anilino) 5-amino 1,2,4-triazole or 3- amlno 5- (meta-acetamido aniline) 1,2,4-triaaole, a (propanamido anilino) amino 1,2,4-triazole, an (acetamido toluido) amino 1,2,4-triazole, an (acetamido xylidino) amino 1,2,4-triazole, a 1- alkyl (e. g., l-methyl, l-ethyl, etc.) (acetamido anilino) amino 1,2,4-triazole, a l-aryl (e. 3., 1- phenvl, l-tolyl, etc.) (acetamldo aniline) amino 1,2,4-triaz o1e, or any other triazole derivative (or mixture thereof) of the kind embraced by Formula I, numerous examples 01' which have been given hereinbeiore and in my copcnding application Serial No. 470,220.

In producing these new condensation products the choice of the aldehyde is dependent largely upon economic considerations and upon the particular properties desired in the finished product. I prefer to use as the aldehydlc reactant formaldehyde or compounds engendering formaldehyde, e. g., paraiormaldehyde, hexamethylene tetramine, etc. Illustrative examples of other sidehydes that may be used are acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, pentaldehyde, heptaiclehyde, capraldehyde, octaldehyde. crotonaldehyde, salicylaldehyde, cinnamaldehyde, benzaldehyde, i'uriural, methaorolein. aldol, glucose, glyoxal, glycollic aldehyde, glyceric aldehyde, etc., mixtures thereof, or mixtures of formaldehyde (or compounds engendering tormaldehyde) with such aldehydes. Illustrative exc. amples or aldehyde-addition products that may be employed instead of the aldehydes themselves are the monoand poly-(N-carbinol) derivatives. more particularly the monoand poly-methylol derivatives oi urea, thicurea, selenourea and iminourea, and of substituted ureas, thioureas. selenoureas and iminoureas (numerous examples or which are given in my ccpending application Serial No, 377,524) monoand poly- (N-canbinol) derivatives of amides of polycarboxylic acids, e. g., maieic, itaconic, iumaric, adipic, malonic, succinic, citric, phthalic, etc., monoand poly- (N-carbinol) derivatives of the amino-triazines, monoand poly-(N-carbinoi) derivatives of the aminodiazines, etc. Particularly good results are obtained with active methylene-containing bodies such as a methylol urea, more particularly monoand di-methylol ureas, and a methyiol aminotriazine, e. g., monomethyloi melamine and polymethylol melamines (di-, tri-, tetra-, pentaand hexa-methylol melamines). Mixtures of aldehydes and aldehyde-addition products may be employed, e. g., mixtures of formaldehyde and methylol compounds such, for instance, as dimethylol urea, trimethylol melamine, hexamethylol melamine, etc.

The ratio 01' the aldehydic reactant to the triazole derivative may be varied over a wide range, but ordinarily the reactants are employed in an amount corresponding to at least one mol of the aldehyde, specifically formaldehyde, for each moi of the triazole derivative. Thus, I may use, for example, from 1 to 7 or 8 or more mols of an aidehyde for each mol of the triazole derivative. Good results are obtained in manufacturing thermosetting resinous compositions using from about 2 to 4 mols aldehyde, specifically formaldehyde, for each moi of the triazole derivative. when the aldehyde is available for reaction in the form of an alkylol derivative, more particularly a methylol derivative such, for instance, as dimethylol urea, trimethylol melamine, etc., then higher amounts of such aldehyde-addition products are used, for instance, from 2 or 3 up to or or more mole of such alkylol derivative for each mol of the triazole derivative.

As indicated hereinbefore, and as i'urther shown by a number of the examples, the properties of the fundamental resins of this invention may be varied widely by introducing other modifying bodies before. during or after eflecting condensation between the primary components. Thus, as modifying agents I may use, for instance, monohydric alcohols such as methyl, ethyl, propyl, isopropyl, isobutyl, hexyl, etc., alcohols; polyhydric alcohols such as diethylene glycol, trlethylene glycol, pentaerythritol, etc.: alcohol-ethers, e. g., ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether. diethylene glycol monobutyl ether, etc.; amides such as formamide, stearamide, acrylamide, benzamide, benzene sulfonamides, toluene sulfonamides, adipic diamide, phthalamide, etc.; amines such as ethylene diamine, phenylene diamine, etc; phenol and substituted phenols, including aminophenols, etc.; ketones, including halogenated ketones; nitriles, including halogenated nitriles: acylated ureas, including halogenated acylated ureas; and others.

The modifying bodies also maize take the form of high molecular weight bodies with or without resinous characteristics, for example, hydrolyzed wood products, formalized cellulose derivatives, lignin, protein-aldehyde condensation products,

aminotriazine-aldehyde condensation products is. 3., melamine-formaldehyde condensation products), aminodiazine-aldehyde condensation products, etc. Other examples of modifying bodies are the urea-aldehyde condensation products, aniline-aldehyde condensation products, furfural condensation products, phenol-aldehyde condensation products, modified or unmodified, saturated or unsaturated polyhydric alcoholpoLvcarboxylic acid condensation products, watersoluble cellulose derivatives, natural gums and resins such as shellac rosin, etc; polyvinyl compounds such as polyvinyl esters, e. g., polyvinyl acetate, polyvinyl butyrate, etc., polyvinyl ethers, including polyvinyl acetals, specifically polyvinyl formal, etc.

Instead of effecting reaction between a triazole derivative of the kind embraced by Formula I and an aldehyde specifically formaldehyde, I may cause an aldehyde to condense with a salt (organic or inorganic) of the triazole derivative or with a mixture of the triazole derivative and a salt thereof. Examples of organic and inorganic acids that may be used in the preparation of such salts are hydrochloric, sulfuric, phosphoric, boric, acetic, chloroacetic, proplonic, butyric, valeric, acrylic, polyacrylic, oxalic, methacrylic, polymethacrylic, malonic, succinic, adipic, malic, maleic, fumaric, benzoic, salicylic, phthalic, camphoric, etc.

Dyes, pigments, plasticizers, mold lubricants, opaciflers and various fillers (e. g., wood flour. glass fibers, asbestos, including defibrated asbestos, mineral wool, mica, cloth cuttings, etc.) may be compounded with the resin in accordance with conventional practice to provide various thermoplastic and thermosetting molding compositions.

The modified and unmodified resinous compositions of this invention have a wide variety of uses. For example, in addition to their use in the production of molding compositions, they may be used as modifiers of other natural and synthetic resins, as laminating varnishes in the production of laminated articles wherein sheet materials, e. g., paper, cloth, sheet asbestos, thin sheets of wood, etc., are coated or coated and impregnated with the resin, superimposed and thereafter united under heat and pressure. They may be employed in the production of wire or baking enamels from which insulated wires and other coated products are made, for bonding or cementing together mica flakes to form a laminated mica article, for bonding together abrasive grains in the preparation of resin-bonded abrasive articles such, for instance, as grindstones, sandpapers, etc., in the manufacture of electrical resistors, etc. They may be used for treating cotton, linen and other cellulosic materials in sheet or other form. They also may be employed as impregnants for electrical coils and for other electrically insulating applications.

What I claim as new and desire to secure by Letters Patent 01' the United States is:

1. A composition of matter comprising the pr duct of reaction of ingredients comprising an aldehyde and a compound corresponding to the general formula where R represents a member of the class con sisting of hydrogen and monovalent hydrocarbon radicals, R. represents a monovalent hydrocarbon radical, and Z represents a member the class consisting oi divalent aromatic and nuclearly halogenated aromatic hydrocarbon radicals.

2. A composition of matter comprising the product of reaction of ingredients comprising tormaldehyde and a compound corresponding to the eneral formula where It represents a member oi the class consisting oi hydrogen and monovaient hydrocarbon radicals, R represents a monovalent hydrocarbon radical, and Z represents a member 01' the class consisting oi divalent aromatic and nuclearly halogenated aromatic hydrocarbon radicals.

8. A composition of matter comprising the product of reaction or ingredients comprising an aldehyde and a compound corresponding to the eneral formula 0 um i 3 NHZNR'-R' member of the class conwhere R represents a sisting of hydrogen and monovalent hydrocarbon radicals, R represents a monovalent hydrocarbon radical, and Z represents a member of the class consisting of divalent romatic and nuclearly halogenated aromatic hydrocarbon radicals.

4. A composition of matter comprising the product of reaction of ingredients comprising an aldehyde and a compound corresponding to the general formula where R represents a monovalent hydrocarbon radical and Z represents a divalent aromatic hydrocarbon radical.

5. A composition of matter comprising the product oi reaction of ingredients comprising an aldehyde and a compound corresponding to the general formula where R represents an alkyl radical and Z represents a divalent aromatic hydrocarbon radical.

6. A composition as in claim 1 wherein the reaction product is the product obtained by efl'ecting initial reaction between the specified components under alkaline conditions.

7. A composition as in claim 1 wherein the reaction product is an alcohol-modified reaction product of the specified components.

8. A heat-curable resinous composition comprising a heat-convertible condensation product of ingredients comprising formaldehyde and a compound corresponding to the general formula o no: E I: nm-z-nn-Ji-w where R represents a monovalent hydrocarbon radical and Z represents a divalent aromatic hydrocarbon radical.

QJUQSOD 9. A product comprising the cured resinous composition of claim 8.

10. A composition comprising the condensation product oi ingredients comprising an aldehyde and an (acetamido aniline) amino 1.2.4-triasole.

11. A resinous composition comprising the product or reaction of ingredients comprising formaldehyde and an (acetamido anilino) amino 1.2.4-triazole.

12. A resinous composition comprising the condensation product of ingredients comprising an aldehyde and a (para-acetamido aniline) amino 1,2,4-triazole.

where R represents a. monovalent hydrocarbon radical and Z represents a divalent aromatic hydrocarbon radio 15. A composition comprising the resinous product of reaction oi ingredients comprising a urea, an aldehyde and an (acetamido anilino) amino 1.2,4-triazole.

16. A composition comprising the product oi reaction of ingredients comprising an aminotriazine, an aldehyde and a compound corresponding to the general formula where R represents a member or the class consisting of hydrogen and monovalent hydrocarbon represents a monovalent hydrocararly halogenated aromatic hydrocarbon radicals.

17. A composition comprising the resinous product of reaction of ingredients com melamine, formaldehyde and a compound corresponding to the general formula where R represents a monovalent hydrocarbon radical and Z represents a divalent aromatic hydrocarbon radical.

18. A heat-curable composition comprising the heat-convertible resinous reaction product of (l) a partial condensation product of ingredients comprising formaldehyde and a compound corresponding to the general formula where R represents a, monovalent hydrocarbon radical and Z represents a divalent aromatic hydrocarbon radical, and (2) a curing reactant. 1o

19. A product comprising the cured composition of claim 18.

20. The method of preparing new synthetic compositions which comprises eflecting reaction between ingredients comprising an aldehyde and a compound corresponding to the general formula CERTIFICATE OF C ORREG 'IION Patent No. 2,58 i,569.

September L 19L 5.

GAETANO F. D'ALELIO.

It is hereby certified that error appears in the printed specification of the above numbered patent requiringcorrection as follows: Page 2, first column, line 58, for "xyenylamino" read --xenylamino-; page 5, first'column, line it, for atoms" read --atomline 5'7, strike out "most" second occurrence; page 14., first column, line '75, after "structure" insert a period; page 6, first column, line 56, after "parts" strike out --of-; line 50, for

80 0." read --80 C.--' and second column, line 10, for "extended" line 12, after "shellac insert a --extender--; page 7, second column,

read

comma; line 19, after "aldehyde" insert a comma; and that the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 22nd day of January, A. D. 19Li6.

(Seal) Leslie Frazer First Assistant Comnissioner of Patents.

comprising formaldehyde and a compound corresponding to the general formula where R represents a, monovalent hydrocarbon radical and Z represents a divalent aromatic hydrocarbon radical, and (2) a curing reactant. 1o

19. A product comprising the cured composition of claim 18.

20. The method of preparing new synthetic compositions which comprises eflecting reaction between ingredients comprising an aldehyde and a compound corresponding to the general formula CERTIFICATE OF C ORREG 'IION Patent No. 2,58 i,569.

September L 19L 5.

GAETANO F. D'ALELIO.

It is hereby certified that error appears in the printed specification of the above numbered patent requiringcorrection as follows: Page 2, first column, line 58, for "xyenylamino" read --xenylamino-; page 5, first'column, line it, for atoms" read --atomline 5'7, strike out "most" second occurrence; page 14., first column, line '75, after "structure" insert a period; page 6, first column, line 56, after "parts" strike out --of-; line 50, for

80 0." read --80 C.--' and second column, line 10, for "extended" line 12, after "shellac insert a --extender--; page 7, second column,

read

comma; line 19, after "aldehyde" insert a comma; and that the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 22nd day of January, A. D. 19Li6.

(Seal) Leslie Frazer First Assistant Comnissioner of Patents. 

